1,1',1"-Nitrilo{tri-2-propyl-tris-[2,2'-ethylidne-bis(4,6-di-tert-butylphen yl)]phosphite} is a compound having the formula I ##STR1##
This compound of formula I is useful as a processing stabilizer for organic polymers as taught in U.S. Pat. Nos. 4,318,845 and 4,374,219. The compound of formula I is disclosed as being a white powder melting at 165.degree.-170.degree. C. The relatively high melting point of the "white powder" form of the compound of formula I as disclosed in the above mentioned patents is a problem when stabilizing organic polymers processed at relatively low temperatures such as blow molding of HDPE and processing of natural rubber. As a result, the additive is not uniformly distributed within the organic polymer causing problems in the stabilization performance of the additive stabilizer.
In accordance with the present invention an amorphous form of the compound of formula I is obtained which does not suffer the problems associated with the higher melting powder reported previously. This new amorphous form is characterized by a glass transition temperature (T.sub.g) within the range of 137.degree.-142.degree. C. free of any endothermic melting peak above 142.degree. C. up to 200.degree. C. as determined by differential scanning calorimetry (DSC). Additionally the amorphous form of the present invention gave a featureless X-ray diffraction pattern obtained using Cu-K.alpha..
Additionally, the new amorphous form of the compound of formula I is organic solvents such a lubricating oils, lubricants and the like. The instant amorphous form not only dissolves more rapidly, but also forms compatible solutions in a short time. This is of enormous practical advantage in many end-use applications.
The instant invention also relates to a process for the preparation of this novel amorphous modification of the compound of formula I.
The instant invention also pertains to a composition stabilized against thermal, oxidative and actinic induced degradation which comprises
(a) an organic material subject to thermal, oxidative or actinic induced degradation, and PA1 (b) an effective stabilizing amount of the amorphous form of 1,1',1"-nitrilo-{tri-2-propyl-tris-[2,2'-ethylidene-bis(4,6-di-tert-butylp henyl)]phosphite}, characterized by a glass transition temperature (T.sub.g) of 137.degree.-142.degree. C. as determined by differential scanning calorimetry (DSC); and by an X-ray diffraction pattern which is featureless. PA1 (a) radical polymerisation (normally under high pressure and at elevated temperature). PA1 (b) catalytic polymerisation using a catalyst that normally contains one or more than one metal of groups IVb, Vb, VIb or VIII of the Periodic Table. These metals usually have one or more than one ligand, typically oxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenyls and/or aryls that may be either .pi.- or .sigma.-coordinated. These metal complexes may be in the free form or fixed on substrates, typically on activated magnesium chloride, titanium(III) chloride, alumina or silicon oxide. These catalysts may be soluble or insoluble in the polymerisation medium. The catalysts can be used by themselves in the polymerisation or further activators may be used, typically metal alkyls, metal hydrides, metal alkyl halides, metal alkyl oxides or metal alkyloxanes, said metals being elements of groups Ia, IIa and/or Ilia of the Periodic Table. The activators may be modified conveniently with further ester, ether, amine or silyl ether groups. These catalyst systems are usually termed Phillips, Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont), metallocene or single site catalysts (SSC). PA1 R.sub.13 has the meaning of R.sub.12 or R.sub.14 is a radical of the formula ##STR3## in which PA1 a) Organic acids, their esters, metal salts and anhydrides, e.g. N-oleoyl-sarcosine, sorbitan-mono-oleate, lead-naphthenate, alkenyl-succinic acids and -anhydrides, e.g. dodecenyl-succinic acid anhydride, succinic acid partial esters and mines, 4-nonyl-phenoxy-acetic acid. PA1 b) Nitrogen-containing compounds, e.g. PA1 c) Phosphorus-containing compounds, e.g. amine salts of phosphonic acid or phosphoric acid partial esters, zinc dialkyldithio phosphates. PA1 d) Sulfur-containing compounds, e.g. barium-dinonyinaphthalene-n-sulfonates, calcium petroleum sulfonates. PA1 e) Derivatives of gamma-alkoxypropylamines described in Japanese Patent Publication No. 15783/1973; and PA1 f) Salts having the formula Y--NH.sub.3 --R.sub.10 CO.sub.2 --in which Y is a group R.sub.11 X.sub.1 CH.sub.2 CH(OH)CH.sub.2 in which R.sub.10 and R.sub.11, independently, are e.g. alkyl and X.sub.1 is O, CO.sub.2, NH, N(alkyl), N(alkenyl) or S, these salts being prepared by mixing an amine Y--NH.sub.2 with an acid R.sub.10 CO.sub.2 H, as disclosed in DE-OS 3437 876 (German Offenlegungsschrift). PA1 g) Compounds having the formula EQU R.sub.12 --X.sub.2 --CH.sub.2 --CH(OH)--CH.sub.2 NR.sub.13 R.sub.14 PA1 h) Compounds having the formula: ##STR12## in which R.sub.15, R.sub.16, R.sub.17 are, independently, hydrogen, C.sub.1 -C.sub.15 alkyl, C.sub.5 -C.sub.12 cycloalkyl, C.sub.6 -C.sub.15 aryl or C.sub.7 -C.sub.12 aralkyl and R.sub.18 R.sub.19, independently, are hydrogen, 2-hydroxyethyl or 2-hydroxypropyl, provided that R.sub.18 and R.sub.19 are not simultaneously hydrogen and, when R.sub.18 and R.sub.19 are each --CH.sub.2 CH.sub.2 OH, R.sub.15 and R.sub.16 are not simultaneously hydrogen and R.sub.17 is not pentyl. These compounds are described in EP Patent specification 0 252 007.
The organic material is preferably a polymer processed at elevated temperatures. Particularly preferred organic polymers are the polyolefins, especially polypropylene and polyethylene, and polyamides. Most particularly the organic polymer is polypropylene.
The compound of this invention is a very effective processing stabilizers for polyolefins than the prior an compounds both in preventing molecular weight changes as well as preventing discoloration.
In general polymers which can be stabilized include
1. Polymers of monoolefins and diolefins, for example polypropylene, polyisobutylene, polybut-1-ene, poly-4-methylpent-1-ene, polyisoprene or polybumdiene, as well as polymers of cycloolefins, for instance of cyclopentene or norbornene, polyethylene (which optionally can be crosslinked), for example high density polyethylene (HDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), branched low density polyethylene (BLDPE). PA0 2. Mixtures of the polymers mentioned under 1), for example mixtures of polypropylene with polyisobutylene, polypropylene with polyethylene (for example PP/HDPE, PP/LDPE) and mixtures of different types of polyethylene (for example LDPE/HDPE). PA0 3. Copolymers of monoolefins and diolefins with each other or with other vinyl monomers, for example ethylene/propylene copolymers, linear low density polyethylene (LLDPE) and mixtures thereof with low density polyethylene (LDPE), propylene/but-1-ene copolymers, propylene/isobutylene copolymers, ethylene/but-1-ene copolymers, ethylene/hexene copolymers, ethylene/methylpentene copolymers, ethylene/heptene copolymers, ethylene/octene copolymers, propylene/butadiene copolymers, isobutylene/isoprene copolymers, ethylene/alkyl acrylate copolymers, ethylene/alkyl methacrylate copolymers, ethylene/vinyl acetate copolymers and their copolymers with carbon monoxide or ethylene/acrylic acid copolymers and their salts (ionomers) as well as terpolymers of ethylene with propylene and a diene such as hexadiene, dicyclopentadiene or ethylidene-norbomene; and mixtures of such copolymers with one another and with polymers mentioned in 1) above, for example polypropylene/ethylene-propylene copolymers, LDPE/ethylene-vinyl acetate copolymers (EVA), LDPE/ethylene-acrylic acid copolymers (EAA), LLDPE/EVA, LLDPE/EAA and alternating or random polyalkylene/carbon monoxide copolymers and mixtures thereof with other polymers, for example polyamides. PA0 4. Hydrocarbon resins (for example C.sub.5 -C.sub.9) including hydrogenated modifications thereof (e.g. tackifiers) and mixtures of polyalkylenes and starch. PA0 5. Polystyrene, poly(p-methylstyrene), poly(.alpha.-methylstyrene). PA0 6. Copolymers of styrene or .alpha.-methylstyrene with dienes or acrylic derivatives, for example styrene/butadiene, styrene/acrylonitrile, styrene/alkyl methacrylate, styrene/butadiene/alkyl acrylate, styrene/butadiene/alkyl methacrylate, styrene/maleic anhydride, styrene/acrylonitrile/methyl acrylate; mixtures of high impact strength of styrene copolymers and another polymer, for example a polyacrylate, a diene polymer or an ethylene/propylene/diene terpolymer, and block copolymers of styrene such as styrene/butadiene/styrene,/isoprene/styrene,/ethylene/butylene/styrene or styrene/ethylene/propylene/styrene. PA0 7. Graft copolymers of styrene or .alpha.-methylstyrene, for example styrene on polybutadiene, styrene on polybutadiene-styrene or polybutadiene-acrylonitrile copolymers; styrene and acrylonitrile (or methacrylonitrile) on polybutadiene; styrene, acrylonitrile and methyl methacrylate on polybutadiene; styrene and maleic anhydride on polybutadiene; styrene, acrylonitrile and maleic anhydride or maleimide on polybutadiene; styrene and maleimide on polybutadiene; styrene and alkyl acrylates or methacrylates on polybutadiene; styrene and acrylonitrile on ethylene/propylene/diene terpolymers; styrene and acrylonitrile on polyalkyl acrylates or polyalkyl methacrylates, styrene and acrylonitrile on acrylate/butadiene copolymers, as well as mixtures thereof with the copolymers listed under 6), for example the copolymer mixtures known as ABS, MBS, ASA or AES polymers. PA0 8. Halogen-containing polymers such as polychloroprene, chlorinated rubbers, chlorinated or sulfochlorinated polyethylene, copolymers of ethylene and chlorinated ethylene, epichlorohydrin homo- and copolymers, especially polymers of halogen-containing vinyl compounds, for example polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride, as well as copolymers thereof such as vinyl chloride/vinylidene chloride, vinyl chloride/vinyl acetate or vinylidene chloride/vinyl acetate copolymers. PA0 9. Polymers derived from a,13-unsaturated acids and derivatives thereof such as polyacrylates and polymethacrylates; polymethyl methacrylates, polyacrylamides and polyacrylonitriles, impact-modified with butyl acrylate. PA0 10. Copolymers of the monomers mentioned under 9) with each other or with other unsaturated monomers, for example acrylonitrile/butadiene copolymers, acrylonitrile/alkyl acrylate copolymers, acrylonitrile/alkoxyalkyl acrylate or acrylonitrile/vinyl halide copolymers or acrylonitrile/alkyl methacrylate/butadiene terpolymers. PA0 11. Polymers derived from unsaturated alcohols and amines or the acyl derivatives or acetals thereof, for example polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate, polyvinyl butyral, polyallyl phthalate or polyallyl melamine; as well as their copolymers with olefins mentioned in 1) above. PA0 12. Homopolymers and copolymers of cyclic ethers such as polyalkylene glycols, polyethylene oxide, polypropylene oxide or copolymers thereof with bisglycidyl ethers. PA0 13. Polyacetals such as polyoxymethylene and those polyoxymethylenes which contain ethylene oxide as a comonomer;, polyacetals modified with thermoplastic polyurethanes, acrylates or MBS. PA0 14. Polyphenylene oxides and sulfides, and mixtures of polyphenylene oxides with styrene polymers or polyamides. PA0 15. Polyurethanes derived from hydroxyl-terminated polyethers, polyesters or polybutadienes on the one hand and aliphatic or aromatic polyisocyanates on the other, as well as precursors thereof. PA0 16. Polyamides and copolyamides derived from diamines and dicarboxylic acids and/or from aminocarboxylic acids or the corresponding lactams, for example polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6/9, 6/12, 4/6, 12/12, polyamide 11, polyamide 12, aromatic polyamides starting from m-xylene diamine and adipic acid; polyamides prepared from hexamethylenediamine and isophthalic or/and terephthalic acid and with or without an elastomer as modifier, for example poly-2,4,4,-trimethylhexamethylene terephthalamide or poly-m-phenylene isophthalamide; and also block copolymers of the aforementioned polyamides with polyolefins, olefin copolymers, ionomers or chemically bonded or grafted elastomers; or with polyethers, e.g. with polyethylene glycol, polypropylene glycol or polytetramethylene glycol; as well as polyamides or copolyamides modified with EPDM or ABS; and polyamides condensed during processing (RIM polyamide systems). PA0 17. Polyureas, polyimides, polyamide-imides and polybenzimidazoles. PA0 18. Polyesters derived from dicarboxylic acids and diols and/or from hydroxycarboxylic acids or the corresponding lactones, for example polyethylene terephthalate, polybutylene terephthalate, poly-1,4-dimethylolcyclohexane terephthalate and polyhydroxybenzoates, as well as block copolyether esters derived from hydroxyl-terminated polyethers; and also polyesters modified with polycarbonates or MBS. PA0 19. Polycarbonates and polyester carbonates. PA0 20. Polysulfones, polyether sulfones and polyether ketones. PA0 21. Crosslinked polymers derived from aldehydes on the one hand and phenols, ureas and melamines on the other hand, such as phenol/formaldehyde resins, urea/formaldehyde resins and melamine/formaldehyde resins. PA0 22. Drying and non-drying alkyd resins. PA0 23. Unsaturated polyester resins derived from copolyesters of saturated and unsaturated dicarboxylic acids with polyhydric alcohols and vinyl compounds as crosslinking agents, and also halogen-containing modifications thereof of low flammability. PA0 24. Crosslinkable acrylic resins derived from substituted acrylates, for example epoxy acrylates, urethane acrylates or polyester acrylates. PA0 25. Alkyd resins, polyester resins and acrylate resins crosslinked with melamine resins, urea resins, polyisocyanates or epoxy resins. PA0 26. Crosslinked epoxy resins derived from polyepoxides, for example from bisglycidyl ethers or from cycloaliphatic diepoxides. PA0 27. Natural polymers such as cellulose, robber, gelatin and chemically modified homologous derivatives thereof, for example cellulose acetates, cellulose propionates and cellulose butyrates, or the cellulose ethers such as methyl cellulose; as well as rosins and their derivatives. PA0 28. Blends of the aforementioned polymers (polyblends), for example PP/EPDM, Polyamide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS, PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates, POM/thermoplastic PUR, PC/thermoplastic PUR, POM/acrylate, POM/MBS, PPO/HIPS, PPO/PA 6.6 and copolymers, PA/HDPE, PA/PP, PA/PPO. PA0 29. Naturally occurring and synthetic organic materials which are pure monomeric compounds or mixtures of such compounds, for example mineral oils, animal and vegetable fats, oil and waxes, or oils, fats and waxes based on synthetic esters (e.g. phthalates, adipates, phosphates or trimellitates) and also mixtures of synthetic esters with mineral oils in any weight ratios, typically those used as spinning compositions, as well as aqueous emulsions of such materials. PA0 30. Aqueous emulsions of natural or synthetic rubber, e.g. natural latex or latices of carboxylated styrene/butadiene copolymers. PA0 31. Polysiloxanes such as the soft, hydrophilic polysiloxanes described, for example, in U.S. Pat. No. 4,259,467; and the hard polyorganosiloxanes described, for example, in U.S. Pat. No. 4,355,147. PA0 32. Polyketimines in combination with unsaturated acrylic polyacetoacetate resins or with unsaturated acrylic resins. The unsaturated acrylic resins include the urethane acrylates, polyether acrylates, vinyl or acryl copolymers with pendant unsaturated groups and the acrylated melamines. The polyketimines are prepared from polyamines and ketones in the presence of an acid catalyst. PA0 33. Radiation curable compositions containing ethylenically unsaturated monomers or oligomers and a polyunsaturated aliphatic oligomer. PA0 34. Epoxymelamine resins such as light-stable epoxy resins crosslinked by an epoxy functional coetherified high solids melamine resin such as LSE-4103 (Monsanto). PA0 2,6-di-tert-butyl-4-methylphenol PA0 2-tert-butyl-4,6-dimethylphenol PA0 2,6-di-tert-butyl-4-ethylphenol PA0 2,6-di-tert-butyl-4-n-butylphenol PA0 2,6-di-tert-butyl-4-i-butylphenol PA0 2,6-di-cyclopentyl-4-methylphenol PA0 2-(.alpha.-methylcyclohexyl)-4,6-dimethylphenol PA0 2,6-di-octadecyl-4-methylphenol PA0 2,4,6-tri-cyclohexylphenol PA0 2,6-di-tert-butyl-4-methoxymethylphenol PA0 2,6-di-tert-butyl-4-methoxyphenol PA0 2,5-di-tert-butyl-hydroquinone PA0 2,5-di-tert-amyl-hydroquinone PA0 2,6-diphenyl-4-octadecyloxyphenol PA0 2,2'-thio-bis-(6-ten-butyl-4-methylphenol) PA0 2,2'-thio-bis-(4-octylphenol) PA0 4,4'-thio- bis-(6- tert-butyl-3-methylphenol ) PA0 4,4'-thio-bis-(6-tert-butyl-2-methylphenol) PA0 2,2'-methylene-bis-(6-tert-butyl-4-methylphenol) PA0 2,2'-methylene-bis-(6-ten-butyl-4-ethylphenol) PA0 2,2'-methylene-bis-[4-methyl-6-(.alpha.-methylcyclohexyl)-phenol] PA0 2,2'-methylene-bis-(4-methyl-6-cyclohexylphenol) PA0 2,2'-methylene-bis-(6-nonyl-4-methylphenol) PA0 2,2'-methylene-bis-[6-(.alpha.-methylbenzyl)-4-nonylphenol] PA0 2,2'-methylene-bis-[6-(.alpha.,.alpha.-dimethylbenzyl)-4-nonylphenol] PA0 2,2'-methylene-bis-(4,6-di-tert-butylphenol) PA0 2,2'-ethylidene-bis-(4,6-di-tert-butylphenol) PA0 2,2'-ethylidene-bis-(6-tert-butyl-4-isobutylphenol)4,4'-methylene-bis-(2,6- di-tert-butylphenol) PA0 4,4'-methylene-bis-(6-tert-butyl-2-methylphenol) PA0 1,1-bis-(5-tert-butyl-4-hydroxy-2-methylphenyl)-butane PA0 2,6-di-(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol PA0 1,1,3-tris-(5-tert-butyl-4-hydroxy-2-methylphenyl)1,1-bis-(5-tert-butyl-4-h ydroxy-2-methylphenyl)-3-n-dodecylmercaptobutane ethyleneglycol bis-[3,3-bis-(3'-tert-butyl-4'-hydroxyphenyl)-butyrate] PA0 di-(3-tert-butyl-4-hydroxy-5-methylphenyl)-dicyclopentadiene PA0 di-[2-(3'-ten-butyl-2'-hydroxy-5'-methyl-benzyl)-6-tert-butyl-4-methylpheny l]terephthalate. PA0 1,3,5-tri-(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene di-(3,5-di-tert-butyl-4-hydroxybenzyl) sulfide PA0 3,5-di-tert-butyl-4-hydroxybenzyl-mercapto-acetic acid isooctyl ester bis-(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithiol terephthalate PA0 1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate PA0 1,3,5-tris-(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate PA0 3,5-di-tert-butyl-4-hydroxybenzyl-phosphoric acid dioctadecyl ester PA0 3,5-di-tert-butyl-4-hydroxybenzyl-phosphoric acid monoethyl ester, calcium-salt PA0 4-hydroxy-lauric acid anilide PA0 4-hydroxy-stearic acid anilide PA0 2,4-bis-octylmercapto-6-(3,5-tert-butyl-4-hydroxyanilino)-s-triazine octyl-N-(3,5-di-tert-butyl-4-hydroxyphenyl)-carbamate PA0 N,N'-di-(3,5-di- tert-butyl-4-hydroxyphenylpropionyl)-hexamethylenediamine PA0 N,N'-di-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-trimethylenediamine PA0 N,N'-di-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hydrazine PA0 diphenylamine, N-phenyl-1-naphthylamine, N-(4-ten-octylphenyl)- 1-naphthylamine, PA0 4,4'-di-tert-octyl-cliphenylamine, reaction product of N-phenylbenzylamine and PA0 2,4,4-trimethylpentene, reaction product of diphenylamine and 2,4,4-trimethylpentene, reaction product of N-phenyl- 1-naphthylamine and 2,4,4-trimethylpentene.
Polyolefins, i.e. the polymers of monoolefins exemplified in the preceding paragraph, preferably polyethylene and polypropylene, can be prepared by different, and especially by the following, methods:
In general, the compounds of the present invention are employed in from about 0.01 to about 5% by weight of the stabilized composition, although this will vary with the particular substrate and application. An advantageous range is from about 0.05 to about 3%, and especially 0.05 to about 1%.
The stabilizer of the instant invention may readily be incorporated into the organic polymers by conventional techniques, at any convenient stage prior to the manufacture of shaped articles therefrom. For example, the stabilizer may be mixed with the polymer in dry powder form, or a suspension or emulsion of the stabilizer may be mixed with a solution, suspension, or emulsion of the polymer. The resulting stabilized polymer compositions of the invention may optionally also contain from about 0.01 to about 5%, preferably from about 0.025 to about 2%, and especially from about 0.1 to about 1% by weight of various conventional additives, such as the materials listed below, or mixtures thereof.